Method for marking a transportation corridor

ABSTRACT

A method for applying a fast curing epoxy traffic marking composition is provided in which curing agents are coated on a carrier such as glass beads or porous silica. These carriers are dropped onto the epoxy coating and promote rapid curing of the top layer of the epoxy coating while the bottom layer is given additional time to adhere to the roadway surface. This enables the application contractor to open a marked roadway in a quicker manner with less motorist disruption.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. provisional Patent ApplicationNo. 61/739,378, filed on Dec. 19, 2012, which is incorporated byreference herein.

BACKGROUND OF THE INVENTION Field of the Invention

This invention relates to the field of epoxy traffic markingcompositions and more particularly to a composition and method forimproving the cure time of such traffic markings.

Description of the Related Art

Epoxy binders currently used in traffic markings consist of two parts.One part (often called resin part or part A) is a formulation containingepoxy monomers or oligomers along with white or yellow pigments. Thesecond part (called part B or hardener) is a formulation of one or morechemicals such as amines, phenols, alcohols or their derivatives. Whentwo parts of resin (part A) and one part of hardener (part B) are mixed,a reaction takes place between the epoxy resin and the hardening agentresulting in a polymerization of epoxy. Once the polymerizationcompletes or nearly completes, the whole mixture become very hard (curedepoxy resin). The mixing ratio of the two parts can vary depending onthe formulation.

These epoxy binders are used in many types of coatings on substrateslike floor, concrete, metal, plastic and other surfaces. They are alsoused as highway traffic markings. Some examples of commercial epoxybinders in traffic markings are LS-50, LS-60, and LS-65 from Epoplexcompany; Poly-Carb Mark 55, Poly-Carb 55.2, Poly-Carb 55.3, Poly-CarbMark 55.4, Poly-Carb Mark 55.6 from Dow Chemicals; Ennis HPS-2, EnnisHPS-3, and Ennis HPS-4 from Flint-Ennis; and the corresponding hardenersare sold under the same name. Epoxy traffic markings offer gooddurability and excellent protection from ultraviolet ray degradation.Epoxy binders, especially slow set epoxy binders, flow well on asphaltand concrete surfaces, fill all gaps in asphalt and concrete surfacesand give a good surface over which retroreflective glass beads can beapplied.

In some applications, it is desirable to speed up the hardening of theepoxy composition through the use of curing agents. In general, manyclasses of chemicals have been used as curing agents for epoxy duringthe past 50 years. Some examples of classes of chemicals are amines,alcohols, phenols, acids, metal salts, and a combination of one or moreof these classes.

U.S. Pat. No. 3,642,649 describes the use of salts prepared fromtertiary amine and acids like hydrobromic acid or toluene sulfonic acidas curing agents. These amine salts cure epoxy resin at low temperatures(40 to 70° F.) which takes several hours to cure.

U.S. Pat. No. 4,162,358 describes the use of aromatic amines as curingagents for epoxy at 80° C. and above.

U.S. Pat. No. 4,273,914 describes the use of carboxylic acid anhydrideand Lewis acid complex as a fast curing agent for epoxy compositions.These are mainly for electrical applications where the Lewis acidcatalysts are from SbCl₅, BF₃, TiCl₄, SnCl₄, and their mixtures. Thecure time at room temperature is more than 36 hours.

U.S. Pat. No. 4,629,742 describes the use of mannich bases(beta-amino-ketones) as curing agents.

U.S. Pat. No. 4,668,736 describes the use of metal salts as curingagents, particularly nitrates and perchlorates. Calcium nitrate isstudied in detail.

U.S. Pat. No. 5,508,373 describes the use of various aliphatic andcycloaliphatic amines as curing agents (hardeners) for epoxy.

U.S. Pat. No. 5,746,935 describes the use of various alcohols and theirderivatives as curing agents for epoxy.

U.S. Pat. No. 5,958,593 describes the use of a mixture of aliphaticamine and metal salt, like calcium nitrate, as a curing agent.

U.S. Pat. No. 6,987,161 describes various mixtures of chemicals ascuring agents for epoxy. The mixtures of chemicals are from classes ofamines, hetero aromatic amines, diamides, primary amines, tertiaryamines, acids, phenols, and alcohols. This patent also teaches how themixture can change the curing temperature and rates.

U.S. Pat. No. 6,911,109 describes how a polymer of acrylic monomer whenmixed with epoxy improves the properties of the final composite. Thecuring agents (hardeners) disclosed are similar to those discussedherein.

U.S. Pat. No. 7,358,312 describes the use of heterocyclic-based aminesand their mixtures with other amines.

SUMMARY OF THE INVENTION

One of the problems with epoxy binders is that it takes several hours toachieve complete curing. When an epoxy binder is used as a roadway linemarking, application contractors must close the road to traffic for morethan 7-8 hours to protect the markings from damage from vehicles. Theapplication cost becomes high as the wait time increases for thecontractors. The wait time also inconveniences the motorists using theroadway.

There is a need for products that will cure the epoxy binders used incoatings applications, especially highway traffic markings, at a fasterrate than the current binders. For ease of application, such productsshould be able to be conveniently applied by contractors.

If the curing agents are instead mixed with the part B hardener, theepoxy layer will cure quickly, but the whole layer will cure fast and nodifference between top and bottom layer will develop. In this situation,the coating layer cures very fast and the binder does not have enoughtime to adhere well onto the roadway surface. In such circumstances, thecured layer will eventually peel off from the asphalt over time.Therefore, the curing agent must be applied after the epoxy layer hasbeen deposited on the roadway surface.

One difficulty with the application of a curing agent is that it must becarefully metered. Given the relatively small amount of curing agentrequired, it is very difficult to control the application of a drop-likeor atomized dispersion of the curing agent.

It has been found that a carrier coated with the curing agent canprovide a controlled mechanism for applying the curing agent to theepoxy coating. By using a carrier, the curing agent can be applied tothe epoxy layer in a similar manner to the application ofretroreflective glass beads used in traffic markings. Such drops wouldinitially start the curing of the epoxy binder at the top of the epoxylayer giving enough time for the lower part of the epoxy layer to adherewell to the roadway surface.

The curing agents used to cure the epoxy resin are known in literatureand discussed in some of the patents referenced above. When these curingagents are dropped on the epoxy layer, curing starts at the top part ofthe layer because of the immediate contact while the bottom part of theepoxy layer is still fluid and slow curing. This permits the bottom partof the epoxy layer to adhere well to asphalt or concrete surfaces. Oncethe top part of the epoxy layer starts curing, the polymerizationreaction slowly descends through the epoxy layer, providing adequatetime for the adhesion of the epoxy layer to the roadway surface.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention proposes to accelerate the curing of the epoxylayer by depositing a carrier containing a curing agent to the epoxylayer. The use of a carrier permits the curing agent to be applied in adrop-like manner so that it starts the curing of the binder layer,usually 15-30 mil wet thickness, from the top while the bottom part ofthe layer has enough time to adhere to asphalt or concrete surface.

This invention offers a convenient solution to this application problemby providing a differential curing rate of the epoxy layer. The top partof the epoxy layer starts coring faster that bottom layer, and the totalcuring is achieved in a shorter time without affecting the adhesionefficiency of the bottom part of the epoxy layer.

The curing agent can be selected from the class of chemicals includingamines, alcohols, acids, and metal salts. These coating agents arecoated on glass beads or porous silica. The coated beads or poroussilica can be dropped onto the epoxy layer by the application contractorfollowed by the application of the retroreflective glass beads.Alternatively, the coated beads or porous silica can be blended with theretroreflective glass beads and applied simultaneously on the epoxy roadmarkings.

The amines used in the coating include aliphatic amines likeethylenediamine, diethylenetriamine, triethylenetetramine,tetraethylenepentamine, 1,6-hexamethylenediamine; cyclic amines likecyclohexyl amines and their derivatives; aromatic amines like benzylamines and their derivatives; and heterocyclic amines like piperazine,imidazole and their derivatives.

The alcohols used in the coating can include aliphatic alcohols orphenols and their derivatives.

The acids used in the coating can include aromatic carboxylic acids,aromatic sulphonic acid and their derivatives.

The metal salts used in the coating can include sodium, potassium, orcalcium nitrates.

Most preferred is a mixture of triethanolamine, piperazine,N-aminoethylpiperine, and diethanolamine in different ratios. Onecommercial product which consists of these chemicals, Accelerator 399from Huntsman Chemicals, has been found to perform well. A solution ofAccelerator 399 in water or isopropyl alcohol was coated on glass beadsor porous silica. The concentration of the solution can be in the rangeof 5-25%, preferably in the range of 10-15%.

The preferred metal salt is calcium nitrate. A solution of calciumnitrate tetrahydrate in water or isopropyl alcohol is preferred. Onecommercial product Accelerator 3130 from Huntsman Chemical which is asolution of calcium nitrate in ethyl alcohol has been used. Theconcentration of the solution can be in the range of 5-25%, preferably10-15%.

The glass beads are in the range of between 20-200 US Mesh, preferablyin the range of 20-150 US mesh. The porous silica has a surface area ofin the range of 1.0 cc/g to 1.9 cc/g, preferably in the range of 1.08cc/g to 1.78 cc/g. The surface area of porous silica ranges from 300m²/g to 400 m²/g, preferably between 320 m²/g to 380 m²/g.

The efficiency of the present invention was determined by droppingcoated glass beads or porous silica on to a slow set epoxy drawdown (6inch×18 inch glass) panel at 40-50° C. and measuring the cure time.Using a wood stick, a line was drawn across the epoxy drawdown atregular intervals and the time taken until the wood stick no longer madea line was noted. At this point, the epoxy layer became too hard for thewood stick to make a line on it. The time difference for complete curingbetween the panel without the coated materials described in thisinvention and the panel with the coated material defines the efficiencyof the curing.

A 50-60% reduction in cure time was observed when chemicals coated onporous silica were used, whereas 20-40% reduction in time was observedwith chemicals coated on glass. The cure time also depends on theinitial temperature when the epoxy binder components (part A and B) aremixed, with higher temperatures correlating with shorter cure times. Ingeneral, contractors apply the epoxy binder for traffic markings between40 to 55° C. It is also noted that the asphalt may have a higher orlower temperature depending on weather.

This invention describes products that can be conveniently applied toepoxy traffic markings as a drop on which facilitates the curing at thetop of the layer first then cure the complete layer at a shorter timecompared to epoxy markings without these products.

Example 1

Accelerator 399 (15 grams) was added to water (7.5 grams) and stirredwell to get a homogeneous solution. 5 grams of this solution were addeddrop wise to 100 grams of glass beads (20-150 US mesh) in a rotatingtumbler while rotating. The dried beads were stored in a closed bottle.

Example 2

Example 1 was repeated except 1,6-hexamethylenediamine was used insteadof Accelerator 399.

Example 3

Accelerator 399 (15 grams) was added to water (7.5 grams) and stirredwell to get a homogeneous solution. 15 grams of this solution were addeddrop wise to 100 grams of porous silica in a rotating tumbler whilerotating. The dried material was stored in a closed bottle.

Example 4

Example 3 was repeated except 1,6-hexamethylenediamine was used insteadof Accelerator 399.

Example 5

5 grams of Accelerator 3130 were added drop wise to 100 grams of glassbeads (20-150 US mesh) in a rotating tumbler while rotating. The driedbeads were stored in a closed bottle.

Example 6

15 grams of Accelerator 3130 were added drop wise to 100 grams of poroussilica in a rotating tumbler while rotating. The dried material wasstored in a closed bottle.

Example 7

Calcium nitrate tetrahydrate (10 grams) was added to water (10 grams)and stirred well to get a homogeneous solution. 20 grams of thissolution were added drop wise to 100 grams of porous silica in arotating tumbler while rotating. The dried material was stored in aclosed bottle.

Example 8

10 grams of polystyrene sulfonic solution in water were added drop wiseto 100 grams of glass beads (20-150 US mesh) in a rotating tumbler whilerotating. The dried beads were stored in a closed bottle.

Experimental

Epoxy resin LS-65 from Epoplex (part A, 30 g) was taken in a plastic cupand warmed to 50° C. in a water bath. The LS-65 hardener (part B, 15 g)was taken in a second cup and warmed to 50° C. A glass panel (6 inch×18inch) was placed on a wood holder and was heated by a heat gun for fewseconds so that the surface of glass warms to about 50-60° C. Part A andpart B of the preheated epoxy resin were mixed using a spatula andpoured onto the warmed glass panel and using a drawdown blade a 25 milwet thickness coating layer was made. The time for complete curing wasmeasured using a wood tongue dispenser and drawing line across the epoxylayer, when no more line can be drawn it is cured. This establishes abaseline curing time.

Method A

The baseline method was repeated to make the epoxy coating layer then 7grams of the coated beads were immediately dropped on the epoxy layerusing a drop box and the time needed for complete curing was observed.The difference in time for complete curing between Method A and thebaseline determines the efficiency of the product.

Method B

The baseline method was repeated to make the epoxy coating layer then 7grams of the coated beads and 18 grams of AASHTO Type I M247 glass beadswere immediately dropped on the epoxy layer using a drop box and thetime needed for complete curing was observed.

The following table shows the curing efficiency of the products of thisinvention from Examples 1-8. All experiments were carried out asdescribed in Methods A or B.

Curing Drop on retro Cure agent coated silica reflective time inExperiment or beads glass beads minutes Control no no 60-70 (base line)Method A Product of example 1 no 45-50 Method A Product of example 2 no45-50 Method A Product of example 3 no 25-30 Method B Product of example3 Type I M247 25-30 Method A Product of example 4 no 30-35 Method AProduct of example 5 no 40-45 Method A Product of example 6 no 20-25Method B Product of example 6 Type I M247 20-25 Method B Product ofexample 7 Type I M247 20-25 Method A Product of example 8 no 35-40

The data show amine or calcium nitrate coated glass beads or poroussilica described in this invention reduce the cure time by about 40-60%.This time will vary if the coating thickness or initial temperature ofepoxy resins changes.

Any documents referenced above are incorporated by reference herein.Their inclusion is not an admission that they are material or that theyare otherwise prior art for any purpose.

Although the invention is illustrated and described herein withreference to specific embodiments, the invention is not intended to belimited to the details shown. Rather, various modifications may be madein the details within the scope and range of equivalents of the claimsand without departing from the invention.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the invention (especially in the context of theclaims) is to be construed to cover both the singular and the plural,unless otherwise indicated herein or clearly contradicted by context.The terms “comprising,” “having,” “including,” and “containing” are tobe construed as open-ended terms (i.e., meaning “including, but notlimited to,”) unless otherwise noted. Recitation of ranges of valuesherein are merely intended to serve as a shorthand method of referringindividually to each separate value falling within the range, unlessotherwise indicated herein, and each separate value is incorporated intothe specification as if it were recited herein.

All methods described herein can be performed in any suitable orderunless otherwise indicated herein or otherwise clearly contradicted bycontext. The use of any and all examples, or exemplary language (e.g.,“such as”) provided herein, is intended merely to better illuminate theinvention and does not pose a limitation on the scope of the inventionunless otherwise claimed. Use of the term “about” should be construed asproviding support for embodiments directed to the exact listed amount.No language in the specification should be construed as indicating anynon-claimed element as essential to the practice of the invention.

Preferred embodiments of this invention are described herein, includingthe best mode known to the inventors for carrying out the invention.Variations of those preferred embodiments may become apparent to thoseof ordinary skill in the art upon reading the foregoing description. Theinventors expect skilled artisans to employ such variations asappropriate, and the inventors intend for the invention to be practicedotherwise than as specifically described herein. Accordingly, thisinvention includes all modifications and equivalents of the subjectmatter recited in the claims appended hereto as permitted by applicablelaw. Moreover, any combination of the above-described elements in allpossible variations thereof is encompassed by the invention unlessotherwise indicated herein or otherwise clearly contradicted by context.

1-19. (canceled)
 20. A method for marking a transportation corridorcomprising the steps of: a. applying an epoxy coating to a surface ofsaid transportation corridor from a dispensing apparatus; and b.applying a curing agent to said epoxy coating, said curing agent beingcoated on a carrier, said coated carrier being dispensed from saiddispensing apparatus.
 21. The method of claim 20 further comprising thestep of: c. applying retroreflective beads to said epoxy coating, saidretroreflective beads being dispensed from said dispensing apparatus.22. The method of claim 21 wherein said retroreflective beads areapplied to said epoxy coating after said coated carrier is applied. 23.The method of claim 21 wherein said retroreflective beads are applied tosaid epoxy coating simultaneous with said coated carrier.
 24. The methodof claim 21 wherein said retroreflective beads and said coated carrierare stored together on said dispensing apparatus.
 25. The method ofclaim 20 wherein said carrier is a glass bead.
 26. The method of claim25 further comprising the step of: c. applying retroreflective beads tosaid epoxy coating, said retroreflective beads being dispensed from saiddispensing apparatus.
 27. The method of claim 26 wherein saidretroreflective beads are applied to said epoxy coating after saidcoated carrier is applied.
 28. The method of claim 26 wherein saidretroreflective beads are applied to said epoxy coating simultaneouswith said coated carrier.
 29. The method of claim 26 wherein saidretroreflective beads and said coated carrier are stored together onsaid dispensing apparatus.
 30. The method of claim 20 wherein saidcarrier is porous silica.
 31. The method of claim 30 further comprisingthe step of: c. applying retroreflective beads to said epoxy coating,said retroreflective beads being dispensed from said dispensingapparatus.
 32. The method of claim 31 wherein said retroreflective beadsare applied to said epoxy coating after said coated carrier is applied.33. The method of claim 31 wherein said retroreflective beads areapplied to said epoxy coating simultaneous with said coated carrier. 34.The method of claim 31 wherein said retroreflective beads and saidcoated carrier are stored together on said dispensing apparatus.